Process of manufacturing substitutes for oils, caoutchouc, resins, and the like.



L. LILIENFELD. PROCESS 0E MANUFACTURING SUBSTITUTES EOE oILS, cAoUTcHoUo, RESINS AND THE LIKE. APPLICATION FILED JUNE 17, 1910. 1,037, l 58.

Patented Aug. 27, 1912.

TVESSES ATTORNEYS 'biviinn sra'ins PATENT oFFicii.

LEON'LILIENFELD, 0F VIENNA, AUSTRIA-HUNGARY.

PROCESS 0F MANUFACTURING SUBSTITUTES FOR OILS', CAUTCHOUC, RESINS, AND

THE LIKE.

To all whom/@'15 may concern.'

Be it known thatI, LEON Lminivrnnn, chemist, of Zeltgasse 1, Vienna, VIII, in the Empire pf Austria-Hungary, have invented {(iylrocess of Manufacturing Substitutes for i s, and I do hereby declare the following to be a full, clear, and exact description of the invention, such as will enable others skilled in the art towhich it appertains to make and use the same.

This invention is based on my observati-on that by treating fats, fatty acids ,or drying oils, particularly -Chinese wood oil or the fatty acids 'of wood oil, or their derivatives or esters derived from fatty acids and higher alcohols, for example lanolin, with amido derivatives or hydroxyl derivatives of aromatic' hydrocarbons or with. transformation products of either of these classes of products, and with condensing agents, masses are obtained which, according to the mode of lpreparation and the quantitative composition of the mixture undergoing reaction, may be used as substitutes for, or admiXtures to, caoutchouc, guttapercha, balata or like substances, or plastic masses of the nature of Celluloid or like products, or resins. I have also found that the condensation may be conducted in presence of glycerin or its derivatives with the result that products are obtained which in respect of their elasticity and solubility are preferable for some purposes to the products -35 obtained in absence of glycerin.

My invention is illustrated in the accompanying drawingforming part of this application, the said drawing being a diagrammatic View to illustrate in general the chemical reaction.

' yIn carrying out the process, the fat, for

instance wood oil, is heated withone or morev amido derivatives or done or more vhydroxyl derivatives of aromatic hydrocarbons, or a mixture of such derivatives, together with a suitable condensing agent such as chlorid of zinc or chlorid of aluminum or the like, iii-presence or absence of water. A smalll proportion of water appears to .be

advantageousl for carrying out the reaction ""if it is desired to avoid development oftoo much energy during'the process. en the reaction is complete'the hot mass is allowed Specification of Letters Patent. Application led June i7, 1910. Serial No. 567,401.

Caoutchouc, Resins, and the Like;

` Patented Aug. 27, 1912.

to cool, whereby it acquires the desired consistence; it may then be washed with water. When glycerin or a derivative thereof is used, the operation differs only in that this material is introduced into the mixture in the desired proportion. v

Thevaromatic derivative which volatilizes during the heating operation may be .suitably condensed for further use; when glyc- Y erin is used some of this volatilizes with the aromatic derivative and may be likewise condensed. The condensation may even be conducted under reduced pressure.

According to the proportion of the aromatic derivative and the condensing agent, and the glycerin, if presentto the fat, such .asvwood oil, and according to the temperature and the duration of the reaction, the product either is a thick'oil or resembles caoutchouc, guttapercha, balata or the like,

or is a plastic mass of the nat-ure of celluloid, horn or resins; it may be used as a substitute for such bodies or as vadmixtures thereto. ,l

The various modifications of the product of the process are more or less transparent and soluble in suitablesolvents. y

VVh'en the products have the consistence of a thick oil, they may bev used, for instance, in the manufacture of varnishes and 'lacquers, "either alone vor in combination with resins or waxes or drying oils and volatile solvents; or they may be used as an addition tovarnishes and lacoluers.l They are'also applicable for water-proofing fabrics, lfor the manufacture of linoleum and'lincrusta, American cloth or the like.

Vhen the products have the general conlsistence of caoutchouc, they may be substituted for thisy material or for guttapercha or balata,

tic and may be used either directly or in solution; their solutions in volatile solvents dry quickly and leave a lustrous residue; they may be used for electric insulation in then form of plates, rings or the like. They are adapted to be rolled, so" that they can be combined with comminuted cork, fibers, covering materials, ground leather or the like, to form linoleum, lincrusta,pAmerican cloth, leather substitutes, driving belts and washers, either by mixing or kneading them with one or the other ofthe aforesaid mateinmany applications; they are elaskneaded, either alone or mixed with one o1' 'Yao rials or a mixture of them, in absence of a solvent, and then rolling the mixture, or by dissolving them, mixing the solution with the said material and applying it to a suitablcsupport. Their solutions can also be applied with a brush and may be used for making water-proof` paper or fabric. In combination with asphalt, pitch, resin, wax, oil or artificial rubber either alone or mixed with each other, they may be used as substitutes for caoutchouc, guttapercha or balata. They may be subjected alone orvadmixed with one or more of the aforesaid substances, to a process of vulcanization by some known agent for the purpose, such as sulfur or sulfur chlorid. They may be more of the aforesaid substances, with caoutchouc or old rubber or guttapercha or balata and used for substitutes forcaoutchouc. In combination with suitable materials such as cellulose either as such or dissolved in. am.- moniacal cupric oxid solution, derivatives of cellulose, like acetylcellulose, nitrocellulose or viscose, glue or albumin, the products may, with or Without the addition of softening agents, be squirted through fine openings vor spinning nozzles for making threads suitable as substitutes 'for spun threads of natural materials like silk. 4By

drying such mixtures in thin layers on sup-- ports fromwhich the dried material can be stripped, films may be obtained which are applicable for photography, among other purposes.

Those products which have the consistence of hard plastic massesor resins, may be used alone or mixed with known plastlcmasses or resins, for purposes to which such plastic masses or resins are applied.

All products obtainable according to the invention may be used for the aforesaid and other purposes either alone or mixed with other materials, for example cellulose and its derivatives such as nitrocellulose, acetylcellulose or viscose; albuminous bodies, such as albumin or casein; glue or gelatin; gums or starches such as gum tragacanth, tragasol, algin, norgin, dextrin, or agar-agar; caoutchouc, balata or gut-tapercha; soft or hard resins, drying oils, fats, waxes or the like; and a softening agent may be present or not. The union of the -products made according to this invention with one or more other materials and softening agents may be effected by mixing. or kneading without the use of any solvent, or the product may be' dissolved and t-he solution mixed with the other material or materials in'an undissolved or a dissolved condition. Notwithstanding that the products are insoluble in `water, they ma., be incorporated with aque A ous solutions of many of the aforesaid bind- `ing agents, such as ammoniaca-l cupric solutions of cellulose, solutions of starch, glue or albumin. This may be necessary for those binding agents which are not soluble in solvents that dissolve thefproducts.

The following examples illustrate the invention:

1. 1 kilo of Chinese wood oil, 1 kilo of orthotoluidin and 60-100 grams of Zinc chlorid, preferably dissolved in 60-100 grams of water, are well mixed together and the mixture is heated to 20G-300 C.l The chemical action in general is illustrated in the drawing. In the figure the circle 1 desifrnates the aromatic substance, 2 the con( ensing agent, 3 the drying oleaginous substance, and 4 the linal product. During the heating operation, samples of the mixture are Withdrawn and allowed to solidify in order to vascertain whether the desired degree -of consistence has been attained. The consistance of a thick oil is very soon attained; after further heating the mixture solidifies, on cooling, to a soft plastic mass,

and after still further heating the consistence on cooling is similar to that of caout; chouc or -guttapercha. In this. condition the mixture which has solidified to the desired product exhibits no stickiness. According to the desired consistence the heating operation is interrupted at the stage in whichthe sample, on cooling, has the desired properties. By still further heating,

a hard product is obtained which in respect of elasticity' and similarity to caoutchouc is considerably inferior to the product at an earlier stage of the heating. The cooled or solidified products are always transparent.,

and if not heated' too long are soluble in many volatile solvents, such as benzene, to luene, turpentine oil, acetone,'alcohol, ether, carbon bisulfid, carbon tetrachlorid, light petroleulm chlorhydrin, vor amyl acetate. The products are soluble in drying and nondrying fats and oils. Should an error have been made 'in judging the sample, vand a product have been' obtained not having the desired consistence, the mass may be relieated until the consistence on cooling is correct.

2. 1 kilo of anilin, l kilo of Chinese wood oil and (l0-100 grams of zinc chlorid, preferably dissolved in 60-100 grams of water are treated inthe manner described '1in Example 1.

3.1 kilo of ortho-toluidin, 1 kilorof' Chinese wood oil, and 60-100 grams of alu'- minium Vchlorid, preferably dissolved in 60- 100 grams of water, are treated in the manner described in Example l.

4. 1 kilo of resorcinol, 1 kilo of Chinese Wood oil and 60-100 grams .of zinc cllorid or aluminum chlorid, preferablydissolvjed in (lO-T00 grams of water, are treated int-he manner described in Example 1. i

5. 1.2 kilos of Chinese wood oil, 1.2 kilos of orthotoluidin, 1.2-3 kilos of glycerin and 752-100 grams of zinc chlorid, preferably dissolved in 72-100 grams` of Water, are well mixed and the mixt-ure is heated to 200"- 3000 C. and further treated as described in 'Example l. The manufacture' o-f hard prod- ,i ing agents, and furthermore they Vresinaceous, or resiniform character. `Nor `doesy the addition of resin oil produce the ucts is facilitated by increasing the proportionof the condensing agent, as illustrated in the following example:

6. 1 kilo of ortho-toluidiml kilo of Chinese wood oil and 150-200 kilos of zinc chlorid,

preferably dissolved in G0400 grains of y are heated together until a test por`- tion on cooling shows a resinous consistence,

water,

whereupon the reaction is interrupted and the mixture allowed to cool.

In the foregoing examples the proportions inay be varied as may be desirablefor obtaining different products. It is impossible to set forth here all the possible com# binations and proportions. Less of the aromatic derivative and more of the Wood oil,

vor less or more of the condensation agent orglycerin may be used in order to obtain different useful products.

I desire tocall particular attention to the fact that the process described herein result-s in different products from those elected by the use merely ofthe oleaginous substance and the condensing agent alone. In other words the aromatic .substance has an important function. .For instance, ifl Chinese Wood oil is heated with zinc chlorid alone, one

can only obtain polymerized wood oil coagu-` lates, which are not soluble in volatile solvshoW no products which are sought by my process,

for when Wood oil, resin oil, and zinc clilorid' are heated together the result is nothing but a thick black smear.

matic substance therefore forms one of the iriain rvfeatures of my invention, since the products formed are soluble in volatile solv'- ents which dry quickly and leave' a lustrous residue. -They are of a resiniform character and can be kept Without coagulation.

What I claim as my invention and desire to secure by Letters Patent is:

l. The herei described'proc'ess of man- 4o` The use of the aro- -f ufacturing compositions of matter which ,v

consists in heating a drying oleaginous substance With an aromatic substance in the presence of a condensing agent.

2. Theherein described process of manil-` sists in heatingwood oil with orthotoluidin in the presence of zinc chlorid.

In testimony whereof lI have signed my name to this specification in the presence of two subscribing witnesses.

Vitnesses:

FRED I. SCHUMANN, AUGUST FUGGER.

LEON LILIENFELD. 

